CN107629301B - High-gloss puncture-resistant low-density polyethylene master batch - Google Patents
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Abstract
The invention discloses a high-gloss puncture-resistant low-density polyethylene master batch which mainly comprises the following raw materials in parts by mass: 100 parts of linear low-density polyethylene, 10-40 parts of low-density polyethylene, 8-46 parts of nano EVA (ethylene-vinyl acetate) composite anti-reflection agent, 0.1-0.5 part of main antioxidant and 0.2-1.0 part of auxiliary antioxidant. The master batch has the characteristics of excellent glossiness, higher puncture resistance and the like.
Description
Technical Field
The invention relates to a low-density polyethylene composition, in particular to a low-density polyethylene master batch with high gloss and puncture resistance.
Background
The linear low-density polyethylene (LLDPE for short) is non-toxic, tasteless and odorless milky white particles with the density of 0.918-0.935 g/cm3. Compared with LDPE, LLDPE has higher softening temperature and melting temperature, has the advantages of high strength, good toughness, high rigidity, good heat resistance and cold resistance, and has good environmental stress crack resistance, impact strength, tear strength and other properties, and is widely applied to manufacturing agricultural films, packaging films, composite films and the like.
As the molecular chain of LLDPE is mainly of a short-chain branched structure, the LLDPE has higher crystallinity and has relatively low transparency all the time. In the practical downstream application process, some manufacturers of electronic product films, automobile protective films and metal surface protective films put forward higher and higher requirements on the transparency of linear polyethylene, and the film material with high gloss can be applied in wider fields. Meanwhile, due to the particularity of the protective film products, the puncture resistance of the film material is required to be high, and the common linear polyethylene products are difficult to combine high glossiness and puncture resistance. In general, the addition of a nucleating agent can increase the crystallinity of the polyethylene film while improving the gloss and transparency of the polyethylene film, and thus the puncture resistance of the material is affected to some extent.
Disclosure of Invention
The invention aims to provide a low-density polyethylene master batch with high gloss and puncture resistance, which has the characteristics of excellent gloss, higher puncture resistance and the like.
The purpose of the invention is realized by the following technical scheme: a low-density polyethylene master batch with high gloss and puncture resistance mainly comprises the following raw materials in parts by mass:
the linear low-density polyethylene resin of the high-gloss puncture-resistant low-density polyethylene master batch can be various types of linear low-density polyethylene resins disclosed by the prior art, the melt flow rate is 0.5-30.0 g/10min, and the density is 0.916-0.930 kg/m3Preferably DNDA-7042 produced by Michelson division of China petrochemical Co., Ltd., melt flow rate of 1.6-2.4 g/10min and density of 0.918-0.922 kg/m3. The addition of a small amount of high-melt-index low-density polyethylene resin is beneficial to improving the processing fluidity and the glossiness of the polyethylene resin.
The low density polyethylene melt flow rate is 1.0-60.0 g/10min, and the density is 0.916-0.925 kg/m3Preferably 868-000-grade materials produced by Mitsuiti-chemical Maotai, Inc., melt flow rate of 43-57 g/10min, density of 0.919-0.922 kg/m3。
Furthermore, the preferable nanometer EVA composite anti-reflection agent is 20-46 parts, and the nanometer EVA composite anti-reflection agent contains 2-20 parts of nucleating agent. The nanometer EVA composite anti-reflection agent comprises EVA, sodium stearate, sodium dodecyl benzene sulfonate, a nucleating agent and hydrated magnesium silicate powder, wherein the mass ratio of the EVA to the sodium stearate to the sodium dodecyl benzene sulfonate is 90-98: 1-5, and the mass ratio of the nucleating agent to the EVA to the hydrated magnesium silicate is 2-20: 3-6.
Specifically, the preparation method of the nano EVA composite anti-reflection agent comprises the following steps: placing 5kg of EVA emulsion with the VA content of 40-60% in a container, dropwise adding sodium stearate and sodium dodecyl benzene sulfonate under stirring, mixing the EVA and sodium stearate and sodium dodecyl benzene sulfonate 90-98: 1-5, then mixing the emulsion with a nucleating agent (Milliken) suspension aqueous solution and a hydrated magnesium silicate powder (Allida) suspension aqueous solution according to a certain dry weight ratio, uniformly stirring, and then performing spray drying by using a spray dryer, wherein the inlet temperature of the spray dryer is 130-180 ℃, the outlet temperature of the spray dryer is 40-70 ℃, and collecting and drying in a cyclone separator to obtain superfine EVA powder rubber containing the nucleating agent, and the particle size of the superfine EVA powder rubber is 50-300 nm.
The EVA emulsion is preferably an organic chemical plant of Beijing Oriental petrochemical engineering Limited company, and is prepared by the following trade marks: BJ-707EVA elastomer emulsion.
The nucleating agent is Milliken HPN-20E.
The main antioxidant is a phenolic antioxidant, and is preferably octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate. The auxiliary antioxidant is phosphate antioxidant, preferably tris (2, 4-di-tert-butylphenyl) phosphite. The slipping agent is erucamide, preferably erucamide of British grass.
The second purpose of the invention is realized by the following technical scheme: the preparation method of the low-density polyethylene master batch with high gloss and puncture resistance comprises the following steps:
(1) placing 5kg of EVA emulsion with the VA content of 40-60% in a container, dropwise adding sodium stearate and sodium dodecyl benzene sulfonate under stirring, mixing the EVA and sodium dodecyl benzene sulfonate 90-98: 1-5, then mixing the emulsion with a nucleating agent suspension aqueous solution and a hydrated magnesium silicate powder suspension aqueous solution according to a certain ratio of dry weight of the emulsion to the nucleating agent suspension aqueous solution and the hydrated magnesium silicate powder suspension aqueous solution, uniformly stirring, then performing spray drying by using a spray dryer, collecting and drying in a cyclone separator, wherein the inlet temperature of the spray dryer is 130-180 ℃, the outlet temperature of the spray dryer is 40-70 ℃, and obtaining superfine EVA powder rubber containing the nucleating agent, and the particle size of the superfine EVA powder rubber is 50-300 nm;
(2) weighing ethylene butylene linear polyethylene resin powder, a nano EVA composite anti-reflection agent, a main antioxidant and an auxiliary antioxidant according to the proportion, and fully mixing in a high-speed mixer for 3-6 min to obtain a mixture;
(3) and (3) adding the mixture obtained in the step (2) into a screw extruder, controlling the temperature of the screw extruder and a die head to be 175-210 ℃, controlling the rotation speed of the screw to be 160-280 rpm, plasticizing, melting, blending, extruding and granulating the mixture to obtain the high-gloss puncture-resistant linear polyethylene resin.
Compared with the prior art, the invention has the following advantages:
1. according to the invention, the high-gloss puncture-resistant linear polyethylene film blow molding material with excellent gloss and higher puncture resistance is developed by compounding the nano-powder EVA and the hydrated magnesium silicate powder to improve the anti-reflection agent and adjusting the formulas of the antioxidant and the auxiliary antioxidant. To obtain a film with the same transparency, the cost of the material provided by the invention is reduced by about 20% compared with the cost of the linear polyethylene resin using the pure anti-reflection nucleating agent. Meanwhile, the film blown by the linear polyethylene material has good glossiness and openness, the puncture resistance is obviously improved, and the film has wider application field.
HPN20E is a commercially available nucleating agent for accelerating the crystallization rate of polyolefin, having better shrinkage stability for PP plastics and a certain anti-reflection effect for LLDPE materials, but the nucleating agent is expensive, and needs a higher addition amount to achieve a more obvious anti-reflection effect, which brings higher cost pressure. The powdery EVA is a rubber phase filling material with good fluidity, the material has good dispersibility, the anti-reflection agent inorganic particles are uniformly dispersed in the rubber phase, the mixing promotes the dispersion effect of the anti-reflection agent HPN20E in plastics, and the addition of a trace amount of hydrated magnesium silicate powder inorganic particles also promotes the heterogeneous nucleation effect, thereby further improving the crystallization rate and the effect of the nucleating agent. Meanwhile, due to the addition of the rubber phase, the toughness of the material is effectively improved, and the inorganic nucleating agent particles are stabilized. Experiments show that compared with LLDPE resin only added with a pure antireflection agent, the LLDPE material prepared by the method has improved stretchability and puncture resistance.
Detailed Description
Preparing a nano EVA composite anti-reflection agent:
preparing a nano EVA composite anti-reflection agent: placing 5kg of EVA emulsion (preferably the EVA elastomer emulsion of BJ-707 manufactured by organic chemical plant of Beijing Oriental petrochemical Co., Ltd.) with VA content of 40-60% into a container, dropwise adding sodium stearate and sodium dodecyl benzene sulfonate (the respective proportions are shown in Table 1) under stirring, mixing with HPN-20E nucleating agent (Milliken) suspension aqueous solution and hydrated magnesium silicate powder (Arinda) suspension aqueous solution according to a certain proportion of the respective dry weights (shown in Table 1), stirring for 2 hours, then adopting a spray dryer to spray dry the EVA powdery rubber with the nucleating agent at the inlet temperature of 170-180 ℃ and the outlet temperature of 60-70 ℃, collecting and drying in a cyclone separator to obtain the EVA powdery rubber containing the nucleating agent with the particle size of 50-300 nm.
Preparing high-gloss puncture-resistant master batch:
(1) weighing linear polyethylene resin, low-density polyethylene resin, nano-powder EVA composite anti-reflection agent, main antioxidant and auxiliary antioxidant according to the proportion in Table 1, and fully mixing in a high-speed mixer for 3-6 min to obtain a mixture.
Wherein the linear polyethylene resin is preferably DNDA-7042 produced by Mitsuitization Mao Ming Branch company, the melt flow rate is 1.6-2.4 g/10min, and the density is 0.918-0.922 kg/m3The low density polyethylene resin is preferably 868-000 produced by Mitsuiti Mitsui Ministry, the melt flow rate is 43-57 g/10min, and the density is 0.919-0.922 kg/m3。
The main antioxidant is octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, and the auxiliary antioxidant is tris (2, 4-di-tert-butylphenyl) phosphite.
(2) And (2) adding the mixture obtained in the step (1) into a screw extruder, controlling the temperature of the screw extruder and a die head to be 175-210 ℃, controlling the rotation speed of the screw to be 160-280 rpm, plasticizing, melting, blending, extruding and granulating the mixture to obtain the high-gloss puncture-resistant polyethylene master batches A-F. . The specific formula is shown in table 1, wherein the contents of all components are calculated by weight parts.
High gloss puncture resistant linear polyethylene composition preparation:
example 1 to example 10:
linear polyethylene resin (MLPE-1810, China petrochemical Min & Min Branch Co., Ltd., melt flow rate of 0.8-1.2g/10min, density of 0.916-0.920 kg/m)3) And adding the high-gloss puncture-resistant polyethylene master batch and the antioxidant into a high-speed mixer, and fully mixing at the speed of 300 r/min for 3-6 min to fully and uniformly mix all the components. And then adding the mixture into a screw extruder, controlling the temperature of the screw extruder and a die head to be 175-210 ℃ and the rotation speed of the screw to be 160-280 rpm, plasticizing, melting, blending, extruding and granulating the mixture to obtain the high-gloss puncture-resistant linear polyethylene resin.
Comparative example 1:
(1) weighing linear low density polyethylene powder (MLPE-1810, Mitsubishi Kangshi, having melt flow rate of 0.8-1.2g/10min and density of 0.916-0.920 kg/m)3) And the main antioxidant and the auxiliary antioxidant are placed in a high-speed stirrer to be fully mixed for 3-6 min, so that all the components are fully and uniformly mixed to obtain a mixture. The specific formula components are shown in table 2, wherein the content of each component is calculated by weight fraction.
Linear low density polyethylene 100 parts
0.2 portion of main antioxidant
0.2 part of auxiliary antioxidant
Wherein the linear polyethylene resin is preferably LLDPE MLPE1810 produced by Miyashi Mao Mingdian, the melt flow rate is 0.8-1.2g/10min, and the density is 0.916-0.920 kg/m3。
The main antioxidant is octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, and the auxiliary antioxidant is tris (2, 4-di-tert-butylphenyl) phosphite.
(2) And (2) adding the mixture obtained in the step (1) into a screw extruder, controlling the temperature of the screw extruder and a die head to be 175-210 ℃, controlling the rotation speed of a screw to be 160-280 rpm, plasticizing, melting, blending, extruding and granulating the mixture to obtain the linear polyethylene resin.
Comparative example 2:
(1) the linear polyethylene powder (MLPE-1810, China petrochemical metallocene division, melt flow rate of 0.8-1.2g/10min, density of 0.916-0.920 kg/m)3) The anti-reflection agent HPN-20E, the main antioxidant and the auxiliary antioxidant are placed in a high-speed stirrer to be fully mixed for 3-6 min, and a mixture is obtained.
Wherein the linear polyethylene resin is preferably LLDPE DNDA-7042 produced by Miyashi Mao Ming Branch of China, the melt flow rate is 1.6-2.4 g/10min, and the density is 0.918-0.922 kg/m3。
The main antioxidant is octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, and the auxiliary antioxidant is tris (2, 4-di-tert-butylphenyl) phosphite.
(2) And (2) adding the mixture obtained in the step (1) into a screw extruder, controlling the temperature of the screw extruder and a die head to be 175-210 ℃, controlling the rotation speed of the screw to be 160-280 rpm, plasticizing, melting, blending, extruding and granulating the mixture to obtain the linear polyethylene anti-reflection master batch G.
(3) Linear polyethylene resin (MLPE-1810, China petrochemical Mitsubishi, Inc., with a bulk flow rate of 0.8-1.2g/10min and a density of 0.916-0.920 kg/m3) And (3) the polyethylene anti-reflection master batch G obtained in the step (2), an antioxidant (the comparative example 2 is that the ratio of the main antioxidant 1010 to the auxiliary antioxidant is 1: 2 parts by mass) into a high-speed mixer, and stirring and blending the components for 3 minutes at the rotating speed of 300 revolutions per minute to fully and uniformly mix the components. Then adding the mixed material into a screw extruder, and controlling the screw extruderAnd performing plasticizing, melting and blending on the mixture at the temperature of 170-210 ℃ and the rotating speed of a screw of 160-280 rpm, and performing extrusion granulation to obtain the linear polyethylene resin.
TABLE 1 composition ratio of master batches
The granulated linear polyethylene product pellets of examples 1 to 10 and comparative examples 1 to 2 were dried at 60 ℃ for 6 hours, and blown into films of 30 μm at 190 ℃ using a single screw film blowing machine, respectively, to perform a performance test. The results are shown in the following table:
TABLE 2 component proportions and Performance test results for examples 1-10 and comparative examples 1-2
From the table, it can be seen that, the method of adding the powder EVA composite anti-reflection agent into the low-density linear polyethylene can obviously improve the turbidity and the glossiness of the LLDPE film, and simultaneously the puncture resistance is improved. Compared with LLDPE master batches only added with the permeability-increasing agent HPN-20E, the composite permeability-increasing agent low-density polyethylene master batches have higher puncture resistance and better comprehensive performance.
The present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof, and the present invention is not limited to the embodiments described above, but rather should be construed broadly within its spirit and scope as defined in the appended claims.
Claims (7)
1. A low-density polyethylene master batch with high gloss and puncture resistance is characterized by mainly comprising the following raw materials in parts by mass:
linear low density polyethylene 100 parts
10-40 parts of low-density polyethylene
8-46 parts of nano EVA (ethylene-vinyl acetate copolymer) composite anti-reflection agent
0.1-0.5 part of main antioxidant
0.2-1.0 part of auxiliary antioxidant;
the nanometer EVA composite anti-reflection agent comprises EVA, sodium stearate, sodium dodecyl benzene sulfonate, a nucleating agent and hydrated magnesium silicate powder, wherein the ratio of the EVA to the sodium stearate to the sodium dodecyl benzene sulfonate is = 90-98: 1-5, and the ratio of the nucleating agent to the EVA to the hydrated magnesium silicate is = 2-20: 3-6 by mass; the nucleating agent is Milliken HPN-20E;
the preparation method of the nano EVA composite anti-reflection agent comprises the following steps: placing 5kg of EVA emulsion with the VA content of 40% -60% in a container, dropwise adding sodium stearate and sodium dodecyl benzene sulfonate under stirring, wherein the ratio of EVA sodium stearate to sodium dodecyl benzene sulfonate = 90-98: 1-5, then mixing the emulsion with a nucleating agent suspension aqueous solution and a hydrated magnesium silicate powder suspension aqueous solution according to a certain dry weight ratio, uniformly stirring, and then performing spray drying by using a spray dryer, wherein the inlet temperature of the spray dryer is 130-180 ℃, the outlet temperature of the spray dryer is 40-70 ℃, and collecting and drying in a cyclone separator to obtain superfine EVA powder rubber containing the nucleating agent, and the particle size of the superfine EVA powder rubber is 50-300 nm.
2. The masterbatch of claim 1, wherein the linear low density polyethylene has a melt flow rate of 0.5-30.0 g/10min and a density of 0.916-0.930 g/cm3。
3. The low-density polyethylene masterbatch with high gloss and puncture resistance according to claim 1, wherein the low-density polyethylene has a melt flow rate of 1.0-60.0 g/10min and a density of 0.916-0.925 g/cm3。
4. The low-density polyethylene masterbatch with high gloss and puncture resistance as claimed in claim 1, wherein the nano EVA composite anti-reflection agent is 20-46 parts, and the nano EVA composite anti-reflection agent contains 2-20 parts of nucleating agent.
5. The low density polyethylene masterbatch with high gloss and puncture resistance according to claim 1, wherein the primary antioxidant is a phenolic antioxidant, and the secondary antioxidant is a phosphite antioxidant.
6. The low density polyethylene masterbatch with high gloss and puncture resistance according to claim 5, wherein the phenolic antioxidant is octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, and the phosphite antioxidant is tris (2, 4-di-tert-butylphenyl) phosphite.
7. The process for preparing the low-density polyethylene masterbatch with high gloss and puncture resistance according to any one of claims 1 to 6, comprising the steps of:
(1) placing 5kg of EVA emulsion with the VA content of 40-60% in a container, dropwise adding sodium stearate and sodium dodecyl benzene sulfonate under stirring, wherein the ratio of EVA sodium stearate to sodium dodecyl benzene sulfonate is = 90-98: 1-5, then mixing the emulsion with a nucleating agent suspension aqueous solution and a hydrated magnesium silicate powder suspension aqueous solution according to a certain dry weight ratio, uniformly stirring, and then performing spray drying by using a spray dryer, wherein the inlet temperature of the spray dryer is 130-180 ℃, the outlet temperature of the spray dryer is 40-70 ℃, and collecting and drying in a cyclone separator to obtain superfine EVA powder rubber containing the nucleating agent, and the particle size of the superfine EVA powder rubber is 50-300 nm;
(2) weighing linear low-density polyethylene, nano EVA composite anti-reflection agent, main antioxidant and auxiliary antioxidant according to the proportion, and placing the materials in a high-speed stirrer for fully mixing for 3-6 min to obtain a mixture;
(3) and (3) adding the mixture obtained in the step (2) into a screw extruder, controlling the temperature of the screw extruder and a die head to be 175-210 ℃, controlling the rotation speed of the screw to be 160-280 rpm, plasticizing, melting, blending, extruding and granulating the mixture to obtain the high-gloss puncture-resistant low-density polyethylene master batch.
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